In this study a number of cage alkenes were synthesised and tested for activity towards ringopening metathesis polymerisation (ROMP) with the commercially available catalysts 55 (Grubbs-I) and 56 (Grubbs-II). The first group of monomers are derivatives of tetracyclo[6.3.0.04,1105,9]undec-2-en-6-one (1). The synthesis of these cage alkenes are summarised in Scheme 7.1. The cage alkene 126b was synthesised by a Diels-Alder reaction between 1 and hexachlorocyclopentadiene (9, Scheme 7.2). The geometry of 126b was determined from XRD data. Knowledge of the geometry of 126b also established the geometry of 127 since conformational changes during the conversion from 126b to 127 are unlikely. Synthesis of the cage alkene 125 by the cycloaddition of 9 to 118 failed. The cage alkene exo-11- hydroxy-4,5,6,7,16,16-hexachlorohexacyclo[7.6.1.03,8.02,13.010,14]hexa-dec-5-ene (124, Scheme 7.3) could therefore not be prepared. Synthesis of 125 by reduction of 126b with various reduction systems was not successful. Theoretical aspects of these reactions were investigated with molecular modelling. A possible explanation for the unreactive nature of 126b towards reduction is presented, but the lack of reactivity of 118 towards 9 eluded clear explanations. The synthesis of cage alkenes from 4-isopropylidenepentacyclo[5.4.0.02,6.03,10.05,9]-undecane-8,11- dione (23) did not meet with much success (Scheme 7.4). Numerous synthetic methods were investigated to affect the transformation from 134a/134b to 135 (Scheme 7.5). These attempts evolved into theoretical investigations to uncover the reasons for the observed reactivity. Possible explanations were established by considering the differences and similarities between the geometries and electronic structures of reactive and unreactive cage alcohols. ROMP of cage monomers based on 1 were mostly unsuccessful. Only the cage monomer 127 showed some reactivity. Endocyclic cage monomers with a tetracycloundecane (TCU) framework showed no reactivity. The results from NMR experiments verified the experimental results. Hexacyclo[8.4.0.02,9.03,13.04,7.04,12]tetradec-5-en-11,14-dione (3) exhibited notable ROMP reactivity. Examination of the orbitals of the cage alkenes used in this study suggested that the reactivity of 1 and 3 could possibly be enhanced by removal of the carbonyl groups. Decarbonylation of 1 and 3 yielded the cage hydrocarbons 159 and 175, respectively. ROMP tests revealed that 175 is an excellent monomer, but 159 was unreactive. The results obtained for the ROMP reactions in this study was rationalised by considering aspects such as ring strain, energy profiles, steric constraints, and frontier orbital theory. The concept of ring strain is less useful when describing the reactivity of cage alkenes towards ROMP and therefore the concepts of fractional ring strain and fractional ring strain energy (RSEf) were developed. A possible link between RSEf and the ROMP reactivity of cage alkenes was also established. The following criteria were put forth to predict the reactivity or explain the lack of reactivity of cage alkenes towards ROMP reactions with Grubbs-I and Grubbs-II. The criteria for ROMP of cage monomers: 1. Sufficient fractional ring strain energy (RSEf). 2. A reasonable energy profile when compared to a reference compound such as cyclopentene. 3. Ability to form a metallacyclobutane intermediate with reasonable distances between different parts of the cage fragment. 4. Sufficient ability of the polymer fragment to take on a conformation that exposes the catalytic site. 5. Sufficient size, shape, orientation and energy of HOMO and/or NHOMO at the alkene functionality of the cage monomer and of the LUMO at the catalytic site. / Thesis (Ph.D. (Chemistry))--North-West University, Potchefstroom Campus, 2012

A systematic study of the surface-initiated polymerisation kinetics of a relatively new type of atom transfer radical polymerisation (ATRP), activators regenerated by electron transfer (ARGET) ATRP, is first demonstrated in this report. Poly(2-hydroxyethyl methacrylate) (PHEMA) and poly(methyl methacrylate) (PMMA) were successfully grown from silicon surfaces at room temperature by surface-initiated ARGET ATRP using a "3rd generation" cationic macroinitiator. The polymer films were analysed by ellipsometry, X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR). With the initial experiment showing that water accelerated conventional ATRP but made it less controlled, the effect of solvent on ARGET ATRP was also evaluated. The living character of ARGET ATRP was demonstrated by successfully reinitiating PHEMA-grafted silicon wafers to grow a second block of PHEMA. Initiator density was shown to have a great effect on the growth rate of PHEMA film thickness on silicon surfaces by comparing the ARGET ATRP growth of PHEMA films using two different initiators, "1st generation" and "3rd generation" cationic macroinitiators, which have different ratios of initiating groups to positive charge. Another type of initiator for ATRP systems, an amide silane, was then investigated as an alternative to polyelectrolyte macroinitiators to avoid degrafting. The effects of solvent, 2, 2′ bipyridyl (bpy) ligand concentration and different types of reducing agent on the growth of PHEMA film from amide-initiator coated silicon wafers by ARGET ATRP were then explored at room temperature. However, it was found that the swings in the uncontrolled laboratory ambient temperature caused inter-sample and inter-experiment variability and so could make the evaluations inaccurate or even wrong. An investigation of temperature on ARGET ATRP showed a dramatic effect on the polymerisation rate. The higher the temperature, the faster the polymerisation proceeded. Therefore, the effects of solvent, ratio of bpy to Cu and reducing agent on the ARGET ATRP growth of PHEMA brushes from amide initiator-coated silicon wafers were re-evaluated at a constant temperature, 30 °C. The development of a polydopamine-based initiator, which was designed to be able to be immobilised on a wide range of surfaces, is then presented in this report. Polydopamine was first shown to be able to deposit on various types of material surfaces by oxidative polymerisation in aqueous solution. Bromoester initiating groups for ATRP systems were incorporated into polydopamine coatings by reacting a fraction of the dopamine monomer with 2-bromoisobutyryl bromide (BIBB) before polymerisation. The modified polydopamine initiator film grew at a comparable rate to unmodified polydopamine, with a 45 nm being grown in 24 hours. Successful incorporation of initiator groups was confirmed by XPS and FTIR, and by the growth of PMMA and PHEMA polymer brushes by ARGET ATRP from the polydopamine initiator coatings. A PMMA brush with a thickness of 239 nm was grown in 72 hours, indicating that the grafting density is sufficiently high to be in the brush regime. This initiator was demonstrated to be able to deposit on a range of substrates, such as metals (steel) and polymers (polystyrene), and successfully initiate polymer growth, demonstrating its broad applicability. The assessment of ARGET ATRP as a simple and effective tool for interfacial shear strength improvement in cellulose-based fibre reinforced thermoplastic composites is finally presented. It was demonstrated by control experiments that grafting polystyrene on glass fibre surfaces via ARGET ATRP greatly improved the interfacial adhesion between glass fibres and a high-impact polystyrene (HIPS) matrix, although a specific value of interfacial strength was not obtained due to failure of the modified glass fibre composite samples in areas other than the interface. It was then demonstrated that PMMA was successfully grown from the surfaces of polydopamine initiator coated cotton fibre and BIBB-modified cotton fibre by ARGET ATRP. Polydopamine initiator was shown to be a better initiator for cotton fibre than BIBB, possibly since the adsorbed water on cotton fibres can react with BIBB. The improvement of interfacial adhesion between cotton fibres and a PMMA matrix by grafting PMMA on the cotton surface was assessed by peel testing of cotton fibres pressed into PMMA sheets. There is a clear trend in the relationship between the peeling force and growth time of PMMA on the cotton fibre by ARGET ATRP, although the inter-sample reproducibility is not good.

Over recent years significant progress has been made in the design and development of late transition metal cationic catalysts for olefin polymerisation. Never-the-less, the activation of catalyst precursors and generation of active species still remains a challenge. In this respect, zwitterionic catalysts could offer a range of advantages over the traditional two component catalytic systems. For example, stable zwitterions are well-defined, single component catalysts which do not require Lewis acid co-catalysts for activation. Therefore, this eliminates the possibility of anions coordinating to the active site and could provide highly active catalysts. Moreover, this could reduce the production costs. In this thesis the 6-aminofulvene-2-aldiminate (AFA) ligand system has been employed to develop zwitterionic, charge-neutral complexes, analogues of Brookhart-type cationic alkene polymerisation catalyst containing 1,2-diimine ligand. Chapter 1 of the thesis provides a comprehensive literature review of the late transition metal (Group 10) α-diimine catalytic systems and the zwitterionic early and late transition metal alkene polymerisation catalysts. Chapter 2 describes the synthesis and characterisation of some novel zwitterionic complexes [(Ph2AFA)Pd(Me)(DMAP)], [(Ph2AFA)(N,N-dimethylbenzylamine-2-C,N)- Pd(II)] and [(Ph2AFA)Ni(η 3-C3H5)] and their possible application as catalyst precursors in alkene polymerisation. In principle, upon activation these complexes should exhibit higher catalytic activity. The ideal catalyst precursor for a highly active palladium based system would be a halide-bridged dimer of the form [(Ph2AFA)Pd(μ-X)]2. Chapter 2 describes several efforts towards the synthesis of such complexes using a range of R2AFA ligands. Even with the introduction of bulky N-substituents such as cyclohexyl or tert-butyl, the halidebridged dimers could not be synthesised. Instead, the reaction between the deprotonated ligand and [PdCl2(NCPh)2] provides bis-chelated complexes [(R2AFA)2Pd]. In order to introduce more steric bulk into the AFAH ligand which might lead to a halide-bridged dimer, two more ligands N,N’-bis(2,6-diisopropyl)phenyl-6-aminofulvene-2-aldimine and N,N’-di-(2,4,6-trimethyl)phenyl-6-aminofulvene-2-aldimine have been synthesised and characterised. It has been found that the presence of the 2,6-diisopropylphenyl substituents in N,N'-bis(2,6-diisopropyl)phenyl-6-aminofulvene-2-aldimine not only prevents the coordination of two ligands to the same metal, but precludes complexation all together. Chapter 2 also describes several efforts to develop a hemi-labile complex for alkene polymerisation. Chapter 3 describes the synthesis of metalloligands of aminofulvene-aldimine (AFA) and corresponding bimetallic complexes. The AFA ligand affords transition metal complexes via both η 5- as well as κ 2-coordination modes. A new synthetic methodology has been developed to synthesise metalloligands [Cp*RuII(Ph2AFA)H][BF4], [Cp*RhIII(Cy2AFA)H][BF4]2 and [Cp*RhIII(Cy2AFA)]- [BF4]. The basicity of the monocationic Rh metalloligand is found to be significantly lower than that of its Ru analogues. This is significant as it opens a potentially easy synthetic route to bimetallic complexes. The bimetallic complex [Cp*RhIII(Cy2AFAPdCl2)][BF4] has been developed for alkene polymerisation in an attempt to investigate the charge effect in alkene polymerisation catalysis. Upon activation this monocationic Rh/Pd bimetallic complex would provide a dicationic active species which would in principle be a more highly active catalyst than the Brookhart mono cationic diimine catalysts. Chapter 4 describes all the experimental procedure and polymerisation tests in this thesis.

Cette thèse a pour but la synthèse de nouveaux polymères par polymérisation anionique et organo-catalyse de polymérisation par activation du monomère. Ce sujet s’articule autour de deux axes majeurs : 1) La synthèse de nouveaux polyamides par activation d’amines aromatiques ou de dérivés acrylamides 2) L’étude de l’ouverture de cycle d’aziridines activées catalysée par les carbènes N-heterocycliques. Le but de cette thèse est donc d’étudier les mécanismes mis en jeu lors de ces polymérisations. Les polymères obtenus seront caractérisés par les méthodes d’analyses classiques (RMN, chromatographie par exclusion stérique, analyses thermiques, spectrométrie de masse, etc.) / In this thesis, the ring-opening polymerization by a monomer activation strategy of heterocyclic monomers such as lactams and aziridines was investigated. In the first part, we described that covalently activated aziridines, i.e. N-sulfonyl aziridines, could be subjected to the N-heterocyclic carbene organocatalyzed ring-opening polymerization (NHC-OROP) in a living/controlled manner. Secondary activated amine, non-activated secondary amine as well as functional initiators were used to promote the ring-opening polymerization of N-activated aziridines. The high tolerance to various chemical functions and the high level of control of the so-called NHC-OROP have allowed the synthesis of well-defined and original aziridine-based block copolymers. On the other hand, the simultaneous combination of anionic ring-opening of ε-caprolactam and condensation reactions of aminobenzoate derivatives was shown to occur in a « one-step » bulk copolymerization allowing the preparation of aliphatic-aromatic copolyamides with enhanced thermal properties (including the glass transition temperature). Alternatively, other methodologies such as covalent activation of lactams with electron withdrawing group or the hydrogen transfer polymerization of acrylamide derivatives were investigated for the synthesis of new polyamides.

A Organização Mundial da Saúde (OMS) relata o câncer como uma das principais causas de morte no mundo. O câncer de próstata é o segundo tipo de câncer mais prevalente em homens, com cerca de 1,1 milhão de casos diagnosticados em 2012. Braquiterapia com iodo-125 é uma método de radioterapia que consiste na introdução de sementes com material radioativo no interior do órgão a ser tratado. As sementes de iodo-125 podem ser inseridas soltas ou em cordas poliméricas bioabsorvíveis, mais comumente o poli(ácido lático-co-ácido glicólico) (PLGA). A função do polímero é reduzir a possibilidade de migração das sementes, o que poderia ser prejudicial para órgãos e tecidos saudáveis. De modo a reduzir os custos do tratamento, a síntese dos dímeros L-lactídeo e glicolídeo, para posterior utilização para preparação do PLGA, por meio da polimerização por abertura de anel, é proposta neste trabalho. Adicionalmente, propõe-se a utilização do amino-alcóxido tris(fenolato) de zircônio (IV) como alternativa ao usual octanoato de estanho (SnOct2), uma vez que a toxicidade do estanho permanece como obstáculo na produção do PLGA para aplicações biomédicas. Embora o iniciador de zircônio seja mais lento do que o SnOct2, massas molares relativamente elevadas foram obtidas quando razões monômero/iniciador (M/I) de 1000/1 (24 h), e 5000/1 (48 h) foram utilizadas. Considerando que as unidades glicolila (GA) são mais reativas do que as unidades lactila (LA), tempos longos de reação são necessários para atingir uma razão LA/GA próxima do objetivo do trabalho (85/15). O grau de racemização também depende do iniciador utilizado. As reações de polimerização realizadas com o iniciador de zircônio mostraram um maior grau de racemização, quando comparadas com aquelas realizadas com o SnOct2. Também foi observado um ligeiro aumento na racemização com o tempo. Considerando os resultados obtidos na síntese e purificação dos dímeros, e na síntese do PLGA em condições semelhantes às industriais, foi possível preparar o polímero de alta massa molar com um custo dezenas de vezes inferior ao custo do PLGA no mercado internacional. Os efeitos da radiação gama no PLGA também foram estudados. Doses normalmente aplicadas para esterilizar materiais para aplicações biomédicas foram empregadas: 10, 18, 25 e 50 kGy. A massa molar de todas as amostras irradiadas diminuiu de uma forma proporcional à dose até 56% de perda para 10 kGy e 72% para 50 kGy porém, são menos pronunciadas para doses mais elevadas. Alterações nas propriedades térmicas, tais como temperatura de fusão, temperatura de transição vítrea e a entalpia de cristalização e fusão foram também observadas após a irradiação. / The World Health Organization (WHO), reports cancer a leading cause of death worldwide. Prostate cancer is the second most common cancer in men, with 1.1 million diagnoses in 2012. Brachytherapy is a method of radiotherapy where encapsulated radioactive sources (seeds) are placed inside or very close to the area requiring treatment. Iodine-125 seeds can be inserted loose or stranded in bioresorbable materials most commonly poly(lactic-co-glycolic) acid (PLGA). The main function of the polymer is to reduce the possibility of seeds migration, which could potentially harm healthy organs and tissues. In order to reduce the cost of the treatment, we propose in this work the synthesis of L-lactide and glycolide dimers, for the production of PLGA using the ring-opening polimerisation route. Additionally, we also propose the use of a Zr (IV) amine tris(phenolate) alkoxide initiator as an alternative to the usual SnOct2, which is still considered an unsolved problem for biomedical applications due to its toxicity. Although the zirconium alkoxide initiator is less active and slower than SnOct2, relatively high molecular weights were obtained at a temperature of 130°C, for a monomer to initiator ratio of 1000/1 (24 h), and 5000/1, in 48 h. Since glycolyl units are more reactive than lactyl counterpart, longer reaction times are needed to achieve a LA/GA ratio closer to the initial (85/15). The degree of racemisation of the polymer depended upon the initiator used. The reactions carried out with the zirconium initiator showed a higher degree of racemisation when compared to those carried out with SnOct2. A modest increase in the degree of racemisation with time was also observed. Considering the results obtained for the synthesis and purification of the dimers, and for the synthesis of PLGA under industrial-like conditions, we concluded that it was possible to produce a high molecular weight polymer that costs far less than the usual price of PLGA on the market. The effects of gamma radiation on PLGA were also studied. We used doses commonly applied to sterilise materials for biomedical applications: 10, 18, 25 and 50 kGy. All irradiated samples showed a reduction in the molecular weight in a dose dependent fashion - up to 56% loss for 10 kGy and 72% for 50 kGy - but these reductions were less pronounced for higher doses. Changes in thermal properties, such as melting point, glass transition temperature and enthalpy of crystallisation and fusion were also observed after irradiation.

The biodegradability and when functionalised biocompatibility of aliphatic polycarbonates (APCs) makes them an attractive class of materials for biomedical applications such as tissue engineering scaffolds and drug-delivery carriers. One route to accessing a wide-range of well-defined and functional APCs is the controlled ring-opening polymerisation (ROP) of cyclic carbonates. In turn, these would ideally be prepared by the direct coupling of CO2 with diols to give water as the only by-product. In this way, the combination of CO2 and sugar-derived diols draws upon two natural renewable building blocks for the construction of polycarbonates that are anticipated to show good biocompatibility properties. Chapter 2 develops a simple and mild alternative to the traditional use of phosgene derivatives for the synthesis of six-membered cyclic carbonates from 1,3-diols and CO2. DFT calculations highlighted the need to lower both the CO2-insertion and ring-closing kinetic barriers to cyclic carbonate formation. Organic superbase, 1,8- diazabicyclo[5.4.0]undec-7-ene (DBU) enabled the formation of carbonate species at 1 atm CO2 pressure whereas, the introduction of a leaving group strategy lowered the cyclisation barrier. Mechanistic considerations suggested a kinetic preference for ring- closing via a nucleophilic addition-elimination pathway rather than a SN2-like intramolecular cyclisation. Chapter 3 applies the procedure with CO2 to the preparation of a novel monomer from natural sugar, ᴅ-mannose. ROP was carried out via an organocatalytic approach and a preference for head-tail linkages in the polycarbonate backbone indicated by NMR spectroscopy and supported by DFT calculations. Chapter 4 utilises CO2 to invert the natural stereochemistry of sugars and create a thymidine-based monomer. The thermodynamic parameters of the ROP with 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) catalyst are determined and the properties of the polycarbonates investigated to include preliminary cell attachment studies. Finally, chapter 5 details the synthesis of cyclic carbonates from 2- deoxy-ᴅ-ribose and the investigation into the different ROP behaviour of the α- and β- anomers. The ability to tune the polymer properties through copolymerisation with trimethylene carbonate (TMC) is also discussed.

The current clinical treatment for bone deficiencies in clinics includes autografts, allografts and bone graft substitutes. All these treatments, however, still have various limitations. Therefore, in this project, we aim to design, synthesise and characterise a new series of novel polymer networks (PNs) to promote bone formation and offer a new therapeutic solution. An innovative polymerisation technique was used to synthesise the novel polymer-based materials. Various lactone monomers were applied with layered double hydroxides (LDHs) as the initiator for the polymerisation. Copolymerisation was used to control the final product degradation rate, microstructure and biocompatibility. SEM and XRD were used to confirm the formation of the 3D polymer microstructure, PNs indicated interconnected fibrous microstructure (thickness of the fibre ranged from 50-150 nm). Up to 90% polymer yield was achieved using thermogravimetric analysis. Both 1H and 13C nuclear magnetic resonance (NMR) were used to understand the effects of monomer combinations in the polymerisation. The effects of the materials on osteosarcoma cell line Saos-2 were investigated. Representative material compositions and their determined mass concentrations were applied using osteogenic culture medium with Saos-2. The PNs have indicated enhanced osteogenesis using varied assays. A poly(lactide-co-caprolactone) PN (monomer mass ratio 1:1) at 6.25 mg/ml, in particular, resulted in enhanced alkaline phosphate activity not only in growth medium but also in osteogenic medium. Moreover, it indicated the highest bone nodule production in area percentage compared to the other PN samples using Saos-2. Mg-substituted calcified extracellular matrix was formed by the use of PN materials. Therefore, this novel PN could have the possibility to be used as an acellular scaffold or a sprinkle-on powder local to defect site to enhance bone formation in vivo. In addition, this novel technology could be used as a scaffold for tissue engineering.

This Thesis describes the activity and mechanism of alkaline earth organohydroborate, tetrahydroborate and alkoxide catalysts for the ring-opening polymerisation (ROP) of cyclic esters including rac-, L-, D- and meso-lactide (LA), and rac-β-butyrolactone (rac-BBL). <b>Chapter One</b> introduces cyclic esters and general mechanisms for their ROP to give polyesters. Living and immortal ROP, an overview of stereocontrolled ROP, and determination of polylactide (PLA) stereosequences are given. Various techniques for polymer characterisations are also described. <b>Chapter Two</b> describes the activity and mechanism of heavy alkaline earth organohydroborate complexes for the ROP of LA. The synthesis and characterisation of alkaline earth alkoxide complexes serving as model species are also described, together with their activities for the ROP of LA. <b>Chapter Three</b> describes the activity and mechanism of a cyclic organohydroborate calcium complex for the ROP of LA. The role of borinic esters as chain transfer agents in the ROP of rac-LA is also discussed. <b>Chapter Four</b> describes the activity and mechanism of heavy alkaline earth tetrahydroborate complexes for the ROP of LA. The immortal ROP of rac-LA using heavy alkaline earth alkoxide complexes and borate esters as chain transfer agents is discussed. <b>Chapter Five</b> describes the activity and mechanism of alkaline earth organohydroborate, tetrahydroborate and alkoxide complexes for the ROP of rac-BBL. <b>Chapter Six</b> presents experimental procedures and characterising data for new complexes reported.

A Organização Mundial da Saúde (OMS) relata o câncer como uma das principais causas de morte no mundo. O câncer de próstata é o segundo tipo de câncer mais prevalente em homens, com cerca de 1,1 milhão de casos diagnosticados em 2012. Braquiterapia com iodo-125 é uma método de radioterapia que consiste na introdução de sementes com material radioativo no interior do órgão a ser tratado. As sementes de iodo-125 podem ser inseridas soltas ou em cordas poliméricas bioabsorvíveis, mais comumente o poli(ácido lático-co-ácido glicólico) (PLGA). A função do polímero é reduzir a possibilidade de migração das sementes, o que poderia ser prejudicial para órgãos e tecidos saudáveis. De modo a reduzir os custos do tratamento, a síntese dos dímeros L-lactídeo e glicolídeo, para posterior utilização para preparação do PLGA, por meio da polimerização por abertura de anel, é proposta neste trabalho. Adicionalmente, propõe-se a utilização do amino-alcóxido tris(fenolato) de zircônio (IV) como alternativa ao usual octanoato de estanho (SnOct2), uma vez que a toxicidade do estanho permanece como obstáculo na produção do PLGA para aplicações biomédicas. Embora o iniciador de zircônio seja mais lento do que o SnOct2, massas molares relativamente elevadas foram obtidas quando razões monômero/iniciador (M/I) de 1000/1 (24 h), e 5000/1 (48 h) foram utilizadas. Considerando que as unidades glicolila (GA) são mais reativas do que as unidades lactila (LA), tempos longos de reação são necessários para atingir uma razão LA/GA próxima do objetivo do trabalho (85/15). O grau de racemização também depende do iniciador utilizado. As reações de polimerização realizadas com o iniciador de zircônio mostraram um maior grau de racemização, quando comparadas com aquelas realizadas com o SnOct2. Também foi observado um ligeiro aumento na racemização com o tempo. Considerando os resultados obtidos na síntese e purificação dos dímeros, e na síntese do PLGA em condições semelhantes às industriais, foi possível preparar o polímero de alta massa molar com um custo dezenas de vezes inferior ao custo do PLGA no mercado internacional. Os efeitos da radiação gama no PLGA também foram estudados. Doses normalmente aplicadas para esterilizar materiais para aplicações biomédicas foram empregadas: 10, 18, 25 e 50 kGy. A massa molar de todas as amostras irradiadas diminuiu de uma forma proporcional à dose até 56% de perda para 10 kGy e 72% para 50 kGy porém, são menos pronunciadas para doses mais elevadas. Alterações nas propriedades térmicas, tais como temperatura de fusão, temperatura de transição vítrea e a entalpia de cristalização e fusão foram também observadas após a irradiação. / The World Health Organization (WHO), reports cancer a leading cause of death worldwide. Prostate cancer is the second most common cancer in men, with 1.1 million diagnoses in 2012. Brachytherapy is a method of radiotherapy where encapsulated radioactive sources (seeds) are placed inside or very close to the area requiring treatment. Iodine-125 seeds can be inserted loose or stranded in bioresorbable materials most commonly poly(lactic-co-glycolic) acid (PLGA). The main function of the polymer is to reduce the possibility of seeds migration, which could potentially harm healthy organs and tissues. In order to reduce the cost of the treatment, we propose in this work the synthesis of L-lactide and glycolide dimers, for the production of PLGA using the ring-opening polimerisation route. Additionally, we also propose the use of a Zr (IV) amine tris(phenolate) alkoxide initiator as an alternative to the usual SnOct2, which is still considered an unsolved problem for biomedical applications due to its toxicity. Although the zirconium alkoxide initiator is less active and slower than SnOct2, relatively high molecular weights were obtained at a temperature of 130°C, for a monomer to initiator ratio of 1000/1 (24 h), and 5000/1, in 48 h. Since glycolyl units are more reactive than lactyl counterpart, longer reaction times are needed to achieve a LA/GA ratio closer to the initial (85/15). The degree of racemisation of the polymer depended upon the initiator used. The reactions carried out with the zirconium initiator showed a higher degree of racemisation when compared to those carried out with SnOct2. A modest increase in the degree of racemisation with time was also observed. Considering the results obtained for the synthesis and purification of the dimers, and for the synthesis of PLGA under industrial-like conditions, we concluded that it was possible to produce a high molecular weight polymer that costs far less than the usual price of PLGA on the market. The effects of gamma radiation on PLGA were also studied. We used doses commonly applied to sterilise materials for biomedical applications: 10, 18, 25 and 50 kGy. All irradiated samples showed a reduction in the molecular weight in a dose dependent fashion - up to 56% loss for 10 kGy and 72% for 50 kGy - but these reductions were less pronounced for higher doses. Changes in thermal properties, such as melting point, glass transition temperature and enthalpy of crystallisation and fusion were also observed after irradiation.

An experimental investigation of the high pressure synthesis of water soluble, self doping conducting polymers is presented. 2- And 3-aminobenzenesulfonic acid and the respective sodium sulfonates have been polymerised. Optimal polymerisation conditions have been determined with respect to yield, conductivity and molecular weight. Reaction parameters such as oxidant, pressure, catalysts, reaction time and temperature and the use of additives were investigated. The minimum pressure required for polymerisation was 7 kbar. An increase in pressure had a negligible effect on polymer characteristics. The polymers were generated in aqueous, non-acidic media, to ensure they were selfdoping when characterised. Conductivities of between 10-6 Scm-1 and 10-3 Scm-1 were measured. The sulfonate salts reacted faster than the sulfonic acids and for both a longer reaction time resulted in higher yields and conductivities. These polymers were completely water soluble, of high molecular weight and able to be cast as thin films. The arylamines 5- and 8-aminonaphthalene-2-sulfonic acid and their respective sodium sulfonates were polymerised at elevated pressure. The naphthalene sulfonate salts polymerised at atmospheric pressure, but displayed a higher molecular weight when reacted under pressure. Generally the naphthalene monomers reacted similarly to the benzene monomers, although there were some differences. Conductivity and yield decreased with increased reaction times and the use of 0.1M equivalents of ferrous sulfate had an negligible effect on the polymers. The polynaphthalenes were highly water soluble, self doping and had conductivities in the order 10-5 to 10-3 Scm-1. A measurement of the activation volume for the polymerisation of 2-methoxyaniline and sodium 8-aminonaphthalene-2-sulfonate was performed. These were determined to be -44 ± 3 cm3mol-1 and -62 ± 10 cm3mol-1 respectively. These large negative values are consistent with rate limiting monomer oxidation.